Negative type light-sensitive silver halide photographic material

ABSTRACT

Disclosed is a negative type light-sensitive silver halide photographic material comprising at least one light-sensitive silver halide emulsion provided on a support, wherein the ratio of silver amount to gelatin amount (Ag/Gel) (wherein the silver amount is the total silver amount in one or more layers provided in the same side as the light-sensitive silver halide emulsion layer with respect to the support, and the gelatin amount is the total gelatin amount in one or more gelatin layers provided in the same side as the light-sensitive silver halide emulsion layer with respect to the support) is 1.0 or more, and a hydrophilic colloid layer in the light-sensitive silver halide emulsion contains a hydrazine compound.

BACKGROUND OF THE INVENTION

This invention relates to a negative type light-sensitive silver halidephotographic material.

In recent years, in the field of printing plates, the developing methodby use of a developer of hydroquinone alone called lith-developing forobtaining an image of high contrast has been the main stream, but thismethod is poor in preservability of the developer, and also since thedeveloping time is long, a rapid access development using phenidone ormetol as the developing agent is incorporated.

However, if such developer is used, the high contrast characteristic oflith-developing will be lost.

Accordingly, so as to have high contrast characteristic comparable withlith-developing in spite of fast processing, the method of adding atetrazolium compound or a hydrazine compound into the film has beenproposed, and it has been reported that an image of high contrast can beobtained by this method even by fast processing with a developing timeof 20 to 30 seconds.

However, the trend of fast processing in recent years is demanding evenultra-fast processing such as shorter than 20 seconds, and also thesituation is such that also the image quality inferior to the presentlevel is not tolerable. When the light-sensitive material of the priorart is subjected to ultra-fast processing with a developing time asshort as 15 seconds by use of a processing solution of the prior art,the amount of the silver developed is small to give no sufficientdensity as unsuitable for practical application.

Further, in this field of art, there is the working of etchingchemically developed silver, which is called "reduction", and the imagedeveloped is demanded to have sufficient amount of silver, and also fromthe standpoint of saving of resources, it is preferable that 90% of thesilver coated should participate effectively in the development.

Thus, it has been desired to have a means which enables development ofsufficient silver amount without waste within a short time and can givean image of high contrast.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a negative typelight-sensitive silver halide photographic material which can solve theabove-mentioned problems, namely capable of developing sufficient amountof silver without waste within a short time, and having an image of highcontrast.

The above object can be accomplished by a negative type light-sensitivesilver halide photographic material comprising at least onelight-sensitive silver halide emulsion provided on a support, whereinthe ratio of silver amount to gelatin amount (Ag/Gel) (wherein saidsilver amount is the total silver amount in one or more layers providedin the same side as said light-sensitive silver halide emulsion layerwith respect to the support, and said gelatin amount is the totalgelatin amount in one or more gelatin layers provided in the same sideas said light-sensitive silver halide emulsion layer with respect to thesupport) is 1.0 or more, and a hydrophilic colloid layer in saidlight-sensitive silver halide emulsion contains a hydrazine compound.

In the present invention, it is desirable that the light-sensitivesilver halide photographic material should contain 2 g/m² or less, morepreferably 0.2 to 1.5 g/m² of a polymer latex therein.

More specifically, the present inventors have found that in order toobtain sufficient density after development processing by ultra-fastprocessing, increase of Ag/Gel should be extremely preferable ratherthan mere increase of the silver amount coated, to have accomplished theabove invention. However, by merely increasing Ag/Gel, there is atendency that cracking may occur when the raw film and the film afterprocessing is stored under low humidity conditions (at relative humidityof 30% or lower) during storage, and hence it has been found that apolymer latex of 2 g/m² or lower should be desirably contained in thelight-sensitive silver halide photographic material. Also, by doing so,the problem of coating irregularity has been reduced.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The specific content of the present invention will be explained below.

The gelatin amount in the present invention is the sum of the gelatinamount in the gelatin layers of one layer or more in the side includingthe light-sensitive silver halide emulsion layer with respect to thesupport (even in the case of the gelatin derivative as described below,the amount of the gelatin derivative is considered as the gelatinamount), and is not limited only to the gelatin amount in the silverhalide emulsion layer. Also, the silver amount is the total silveramount in the respective layers, when it is provided by coating in aplural number of layers in the same side with respect to the support.

The hydrazine compound to be used in the present invention may includecompounds represented by the following formula [I], [I-a], [I-b]or[I-c]. ##STR1## wherein R¹ and R² each represent hydrogen atom, amonovalent aromatic residue, a monovalent heterocyclic residue or amonovalent aliphatic residue, Q₁ and Q₂ each represent hydrogen atom, analkylsulfonyl group which may be substituted or unsubstituted, anarylsulfonyl group which may be substituted or unsubstituted, and Xlrepresents oxygen atom or sulfur atom. ##STR2## wherein R₁ and R₂ eachrepresent an aryl group or a heterocyclic group, R represents a divalentorganic linking group, n is 0 to 6, m is 0 or 1, and when n is 2 ormore, respective R's may be either the same or different. ##STR3##wherein R₂₁ represents an aliphatic group, an aromatic group or aheterocyclic group, R₂₂ represents hydrogen atom, an alkoxy group whichmay be substituted, a heterocyclic oxy group, an amino group or anaryloxy group, P₁ and P₂ each represent hydrogen atom, an acyl group ora sulfinic acid group. ##STR4## wherein Ar represents an aryl groupcontaining at least one of diffusion resisitant group or silver halideadsorption promoting group, and R₃₁ represents a substituted alkylgroup.

Of the hydrazine compounds represented by Formula [I] to be used in thepresent invention, the compounds wherein X₁ is oxygen atom and R² ishydrogen atom are particularly preferred.

As the monovalent organic residue of the above R¹ and R², aromaticresidues, heterocyclic residues and aliphatic residues are included.

As the aromatic residues, there may be included phenyl group, naphthylgroup and these groups having substituents (e.g. alkyl, alkoxy,acylhydrazino, dialkylamino, alkoxycarbonyl, cyanol, carboxyl, nitro,alkylthio, hydroxy, sulfonyl, carbamoyl groups, halogen atoms,acylamino, sulfonamide, thiourea groups, etc ). Specific examples havingsubstituents may include 4-methylphenyl, 4-ethylphenyl,4-oxyethylphenyl, 4-dodecylphenyl, 4-carboxyphenyl,4-diethylaminophenyl, 4-octylaminophenyl, 4-benzylaminophenyl,4-acetamido-2-methylphenyl,4-(3-ethylthioureido)phenyl,4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl,4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl groups, etc.

As the heterocyclic groups, 5-membered or 6-membered monocyclic or fusedrings having at least one of oxygen, nitrogen, sulfur or selenium atommay be included, and these may have substituents. Specific examples mayinclude residues such as pyrroline, pyridine, quinoline, indole,oxazole, benzooxazole, naphthoxazole, imidazole, benzoimidazole,thiazoline, thiazole, benzothiazole, naphthothiazole, selenazole,benzoselenazole, naphthoselenazole rings, etc.

These heterocyclic rings may be also substituted with alkyl groupshaving 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms,aryl group having 6 to 18 carbon atoms, halogen atoms, alkoxycarbonylgroup, cyano group, amide group, etc.

As the aliphatic residues, straight and branched alkyl groups,cycloalkyl groups and these groups attached with substituents, as wellas alkenyl and alkynyl groups are included.

Examples of the straight or branched alkyl group may include alkylgroups having 1 to 18, preferably 1 to 8 carbon atoms, specificallymethyl, ethyl, isobutyl, 1-octyl groups and the like.

Examples of the cycloalkyl group may include those having 3 to 10 carbonatoms, specifically cyclopropyl, cyclohexyl, adamantyl groups and thelike. As the substituent on the alkyl group or the cycloalkyl group,there may be included alkoxy, alkoxycarbonyl, carbamoyl, hydroxy,alkylthio, amide, acyloxy, cyano, sulfonyl groups, halogen atoms, arylgroups, etc., and specific examples of those substituted can include3-methoxypropyl, ethoxycarbonylmethyl, 4-chlorocyclohexyl, benzyl,p-methylbenzyl, p-chlorobenzyl groups, etc.

As the alkenyl group, for example, allyl group, and as the alkynylgroup, propargyl group may be included.

Specific examples of the hydrazine compound to be used in the presentinvention are shown below, but the present invention is not limited bythese at all.

(I-1)1-Formyl-2-{4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl}hydrazine

(I-2)1-Formyl-2-{4-[2-(2,4-di-tert-butylphenoxy)butylureido]phenyl}hydrazine

(I-3) 1-Formyl-2-(4-diethylaminophenyl)hydrazine

(I-4) 1-Formyl-2-(p-tolyl)hydrazine

(I-5) 1-Formyl-2-(4-ethylphenyl)hydrazine

(I-6) 1-Formyl-2-(4-acetamido-2-methylphenyl)hydrazine

(I-7) 1-Formyl-2-(4-oxyethylphenyl)hydrazine

(I-8) 1-Formyl-2-(4-N,N-dihydroxyethylaminophenyl)hydrazine

(I-9) 1-Formyl-2-(4-(3-ethylthioureido)phenyl)hydrazine

(I-10)1-Thioformyl-2-(4-[2-(2,4-di-tert-butylphenoxy)-butylamido]phenyl)hydrazine

(I-11) 1-Formyl-2-(4-benzylaminophenyl)hydrazine

(I-12) 1-Formyl-2-(4-octylaminophenyl)hydrazine

(I-13) 1-Formyl-2-(4-dodecylphenyl)hydrazine

(I-14)1-Acetyl-2-{4-[2-(2,4-di-tert-butylphenoxy)-butylamido]phenyl}hydrazine

(I-15) 4-Carboxyphenylhydrazine

(I-16) 1-Acetyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine

(I-17) 1-Ethoxycarbonyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine

(I-18) 1-Formyl-2-(4-hydroxyphenyl)-2-(4-methylphenylsulfonyl)hydrazine

(I-19) 1-(4-Acetoxyphenyl)-2-formyl-1-(4-methylphenylsulfonyl)hydrazine

(I-20) 1-Formyl-2-(4-hexanoxyphenyl)-2-(4-methylphenylsulfonyl)hydrazine

(I-21)1-Formyl-2-[4-(tetrahydro-2H-pyran-2-yloxy)phenyl]-2-(4-methylphenylsulfonyl)hydrazine

(I-22)1-Formyl-2-(4-(3-hexylureidophenyl))-2-(4-methylphenylsulfonyl)hydrazine

(I-23)1-Formyl-2-(4-methylphenylsulfonyl)-2-[4-(phenoxythiocarbonylamino)phenyl]hydrazine

(I-24)1-(4-Ethoxythiocarbonylaminophenyl)-2-formyl-1-(4-methylphenylsulfonyl)hydrazine

(I-25)1-Formyl-2-(4-methylphenylsulfonyl)-2-[4-(3-methyl-3-phenyl-2-thioureido)phenyl]hydrazine

(I-26)1-{{4-{3-[4-(2,4-bis-t-amylphenoxy)butyl]ureido}phenyl}}-2-formyl-1-(4-methyl-phenylsulfonyl)hydrazine##STR5##

Next, Formulae [I - a], [I -b] and [I - c] are to be described in moredetail below. ##STR6## In the formula, R₁ and R₂ each represent an arylgroup or a heterocyclic group, R represents a divalent organic linkinggroup, and n represents 0 to 6 and m represents 0 or 1.

Here, the aryl group represented by R₁ and R₂ may include phenyl group,naphthyl group, and the heterocyclic group represented by R₁ and R₂ mayinclude pyridyl group, benzothiazolyl group, quinolyl group, thienylgroup, etc., but R₁ and R₂ may be preferably aryl groups. The aryl groupor heterocyclic group represented by R₁ and R₂ can introduce varioussubstituents therein. Examples of substituents may include halogen atoms(e.g. chlorine, fluorine, etc.), alkyl groups (e.g. methyl, ethyl,dodecyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, isopropoxy, butoxy,octyloxy, dodecyloxy, etc.), acylamino groups {e.g. acetylamino,pivalylamino, benzoylamino, tetradecanoylamino α-(2 4-di-t-amylphenoxy)butyrylamino. etc.}, sulfonylamino groups (e.g. methanesulfonylamino,butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.),urea groups (e.g. phenylurea, ethylurea, etc.), thiourea groups (e.g.phenylthiourea, ethylthiourea, etc.), hydroxy group, amino group,alkylamino groups (e.g. methylamino, dimethylamino, etc.), carboxygroup, alkoxycarbonyl groups (e.g. ethoxycarbonyl), carbamoyl group,sulfo group and so on. Examples of the divalent organic linking grouprepresented by R may include alkylene groups (e.g. methylene, ethylene,trimethylene, tetramethylene, etc.), arylene groups (e.g. phenylene,naphthylene, etc.), aralkylene groups, etc., and the alkylene group maycontain oxy group, thio group, seleno group, carbonyl group, ##STR7##group (R₃ represents hydrogen atom, an alkyl group, an aryl group),sulfonyl group, etc. in the bond. Into the group represented by R can beintroduced various substituents.

Examples of substituents may include --CONHNHR₄ (R₄ has the same meaningas R₁ and R₂ as described above), alkyl groups, alkoxy groups, halogenatoms, hydroxy group, carboxy group, acyl groups, aryl groups, etc.

R may be preferably a alkylene group.

Of the compounds represented by Formula [I - a], preferable arecompounds wherein R¹ and R² are substituted or unsubstituted phenylgroups, n=m=1 and R represents an alkylene group.

Representative compounds represented by the above Formula [I - a] areshown below. ##STR8##

In the following, Formula [I - b] is to be described. ##STR9## Thealiphatic group represented by R₂₁ may be preferably one having 6 ormore carbon atoms, particularly a straight, branched or cyclic alkylgroup having 8 to 50 carbon atoms. Here, the branched alkyl group may becyclized so as to form a saturated hetero ring containing one or morehetero atoms. The alkyl group may have substituent such as aryl group,alkoxy group, sulfoxy group, etc.

The aromatic group represented by R₂₁ is a monocyclic or bicyclic arylgroup or unsaturated heterocyclic group. Here, the unsaturatedheterocyclic group may be condensed with the monocyclic or bicyclicgroup to form a heteroaryl group.

For example, there may be included benzene ring, naphthalene ring,pyridine ring, pyrimidine group, imidazole ring, pyrazole ring,quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring,benzothiazole ring, etc., but amount them those containing benzene ringare preferred.

As R₂₁, particularly preferred is an aryl group.

The aryl group or unsaturated heterocyclic group represented by R₂₁ maybe substituted, and representative substituents may include straight,branched or cyclic alkyl groups (preferably monocyclic or bicyclic oneswith an alkyl moiety having 1 to 20 carbon atoms), alkoxy groups (havingpreferably 1 to 20 carbon atoms), substituted amino groups (preferablyamino groups substituted with alkyl groups having 1 to 20 carbon atoms),acylamino groups (having preferably 2 to 30 carbon atoms), sulfonamidegroups (having preferably 1 to 30 carbon atoms), ureido groups (havingpreferably 1 to 30 carbon atoms) and others.

Of the groups represented by R₂₂ in the formula [I - b], the alkoxygroup which may be substituted may have 1 to 20 carbon atoms and may besubstituted with halogen atoms, aryl groups, etc.

Of the groups represented by R₂₂ in the formula [I - b], the aryloxygroup or the heterocyclic oxy group which may be also substituted may bepreferably monocyclic, and the substituent may include halogen atoms,alkyl groups, alkoxy group, cyano group, etc.

Of the groups represented by R₂₂, preferable are alkoxy groups or aminogroups which may be also substituted.

In the case of an amino group, A₁ and A₂ in the group ##STR10## groupmay be an alkyl group, alkoxy group which may be substituted, or acyclic structure containing --O--, --S--, --N-- group bond. However, R₂₂cannot be hydrazino group.

R₂₁ or R₂₂ in Formula [I - b] may be one having a ballast groupconventionally used in the immobile additive for photography such ascoupler, etc. incorporated therein. The ballast group is a group having8 or more carbon atoms relatively inert to photographic characteristic,and can be chosen from, for example, alkyl groups, alkoxy groups, phenylgroups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups, etc.

R₂₁ or R₂₂ in Formula [I- b] may be also one having a group forstrengthening adsorption to the surface of silver halide grainsincorporated therein. As such adsorptive groups, there may be includedthe groups as disclosed in U.S. Pat. No. 4,355,105 such as thioureagroup, heterocyclic thioamide group, mercaptoheterocyclic group,triazole group, etc. Among the compounds represented by the group [I -b], the compounds represented by Formula [I - b - a] are particularlypreferable. ##STR11## In the Formula [I - b - a],

R₂₃ and R₂₄ each represent hydrogen atom, an alkyl group which may besubstituted (e.g. methyl, ethyl, butyl, dodecyl, 2-hydroxypropyl,2-cyanoethyl, 2-chloroethyl group), a phenyl, naphthyl, cyclohexyl,pyridyl, pyrrolidyl group which may be substituted (e.g. phenyl,p-methylphenyl, naphthyl, α-hydroxy-naphthyl, cyclohexyl,p-methylcyclohexyl, pyridyl, 4-propyl-2-pyridyl, pyrrolidyl,4-methyl-2-pyrrolidyl group);

R₂₅ represents hydrogen atom or a benzyl, alkoxy and alkyl group whichmay be substituted (e.g. benzyl, p-methylbenzyl, methoxy, ethoxy, ethyl,butyl group);

R₂₆ and R₂₇ each represent a divalent aromatic group (e.g. phenylene ornaphthylene group), Y represents sulfur atoms or oxygen atom, Lrepresents a divalent linking group (e.g. --SO₂ CH₂ CH₂ NH--SO₂ NH--,--OCH₂ SO₂ NH--, --O--, --CH═N--);

R₂₈ represents --NR'R" or --OR₂₉ ;

R', R" and R₂₉ each represent hydrogen atom, an alkyl group which may besubstituted (e.g. methyl, ethyl, dodecyl group), a phenyl group whichmay be substituted (e.g. phenyl, p-methylphenyl, p-methoxyphenyl group)or a naphthyl group which may be substituted (e.g. α-naphthyl group,β-naphthyl group), m, n represent 0 or 1, and when R₂₈ represents OR₂₉,Y should preferably represent sulfur atom.

Representative compounds represented by the above Formulae [I - b] and[I - b - a] are shown below.

Specific compounds of Formula [I-b]: ##STR12## Of the above specificcompounds, by taking examples of the compounds I-b-45 and I-b-47, theirsynthetic methods are shown below. ##STR13##

A mixture of 153 g of 4-nitrophenylhydrazide and 500 ml ofdiethyloxalate is refluxed for one hour. While the reaction isproceeded, ethanol is removed and finally the mixture is cooled toprecipitate crystals. After filtration, the product is washed severaltimes with petroleum ether and recrystallized. Then, 50 g of thecrystals (A) obtained are dissolved by heating in 1000 ml of methanol,and reduced in a H₂ atmosphere pressurized at 50 psi in the presence ofPd/C (palladium-carbon) catalyst to obtain the compound (B).

To a solution of 22 g of the compound (B) dissolved in 200 ml ofacetonitrile and 16 g of pyridine is added an acetonitrile solutioncontaining 24 g of the compound (C) at room temperature. After theinsolubles are filtered off, the filtrate is concentrated and purifiedby recrystallization to obtain 31 g of the compound (D).

Thirty (30) g of the compound (D) is hydrogenated similarly as describedabove to obtain 20 g of the compound (E).

To a solution of 10 g of the compound (E) dissolved in 100 ml ofacetonitrile is added 3.0 g of ethylisothio-cyanate, and the mixture isrefluxed for one hour. After evaporation of the solvent, the residue ispurified by recrystallization to obtain 7.0 g of the compound (F). To asolution of 5.0 g of the compound (F) dissolved in 50 ml of methanol isadded methylamine (8 ml of aqueous 40% solution), followed by stirring.After concentrating slightly methanol, the precipitated solid is takenout and purified by recrystallization to obtain Compound I - b - 45.##STR14##

Into a stirred solution of 22 g of the compound (B) dissolved in 200 mlof pyridine, 22 g of p-nitrobenzenesulfonyl chloride is added. Thereaction mixture is poured into water, and the post-precipitated solidis taken out to obtain the compound (C). From the compound (C),according to the same reactions as in the case of Compound I - b - 45following the synthesis scheme, Compound I - b - 47 is obtained.

Next, Formula [I - c] is to be described. ##STR15##

In Formula [I - c], Ar represents an aryl group containing at least oneof diffusion resistant groups or silver halide adsorption promotinggroups, and as the diffusion resistant group, a ballast groupconventionally used in immobile additives for photography such ascoupler, etc. is preferable. The ballast group is a group having 8 ormore carbon atoms relatively inert to photographic characteristic, andcan be chosen from, for example, alkyl groups, alkoxy groups, phenylgroups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups, etc.

As the silver halide adsorption promoting group, there may be includedthe groups as disclosed in U.S. Pat. No. 4,385,108 such as thioureagroup, thiourethane group, heterocyclic thioamide group,mercaptoheterocyclic group, triazole group, etc.

R₃ represents a substituted alkyl group, and the alkyl group may be astraight, branched or cyclic alkyl group, including methyl, ethyl,propyl, butyl, isopropyl, pentyl, cyclohexyl and the like.

As the substituent to be introduced into these alkyl group, there may beincluded groups of alkoxy (e.g. methoxy, ethoxy), aryloxy (e.g. phenoxy,p-chlorophenoxy), heterocyclic oxy (e.g. pyridyloxy), mercapto,alkylthio (e.g. methylthio, ethylthio), arylthio (e.g. phenylthio,p-chlorophenylthio), heterocyclic thio (e.g. pyridylthio, pyrimidylthio,thiadiazolylthio), alkylsulfonyl (e.g. methanesulfonyl, butanesulfonyl),arylsulfonyl (e.g. benzenesulfonyl), heterocyclic sulfonyl (e.g.pyridylsulfonyl, morpholinosulfonyl), acyl (e.g. acetyl, benzoyl),cyano, chloro, bromo, alkoxycarbonyl (e.g. ethoxycarbonyl,methoxycarbonyl), aryloxycarbonyl (e.g. phenoxycarbonyl), carboxy,carbamoyl, alkylcarbamoyl (e.g. N-methylcarbamoyl,N,N-dimethylcarbamoyl), arylcarbamoyl (e.g. N-phenylcarbamoyl), amino,alkylamino (e.g. methylamino, N,N-dimethylamino), arylamino (e.g.phenylamino, naphthylamino), acylamino (e.g. acetylamino, benzoylamino),alkoxycarbonylamino (e.g. ethoxycarbonylamino), aryloxycarbonylamino(e.g. phenoxycarbonylamino), acyloxy (e.g. acetyloxy, benzoyloxy),alkylaminocarbonyloxy (e.g. methylaminocarbonyloxy),arylaminocarbonyloxy (e.g. phenylaminocarbonyloxy), sulfo, sulfamoyl,alkylsulfamoyl (e.g. methylsulfamoyl), arylsulfamoyl (e.g.phenylsulfamoyl), etc.

The hydrogen atom of hydrazide may be also substituted with asubstituent such as sulfonyl group (e.g. methanesulfonyl,toluenesulfonyl), acyl group (e.g. acetyl, trifluoroacetyl), oxalylgroup (e.g. ethoxalyl), etc.

Representative compounds represented by the above Formula [I - c] areshown below. ##STR16##

Next, a synthesis example of Compound I - c - 5 is described. ##STR17##

According to the procedure similar to the synthetic method of CompoundI - b - 45, Compound I - c - 5 is obtained.

The position where the above hydrazine compound is to be added is in thesilver halide emulsion layer and/or the non-light-sensitive layerexisting on the silver halide emulsion layer on the support, butpreferably in the silver halide emulsion layer and/or its subbing layer.

The amount added should be preferably 10⁻⁵ to 10⁻¹ mole/1 mole ofsilver, further preferably 10⁻⁴ to 10⁻² mole/1 mole of silver.

In the present invention, it is preferable to use light-sensitive silverhalide grains with an average grain size of 0.05 to 0.3μ. Here, theaverage grain size refers to its diameter in the case of sphericalparticles, or the diameter when calculated on the circular image withthe same area as its projected image in the case of grains with shapesother than spherical shape.

It is preferred that 60% or more of the total grains should haveparticle sizes within the range of ±10% of the average grain size.

For the silver halide emulsion to be used in the present invention(hereinafter called silver halide emulsion or merely emulsion), any ofsilver bromide, silver iodobromide, silver iodochloride, silverchloroiodobromide, silver chloride, silver chlorobromide, silver iodidemay be used. Also, the silver halide emulsion used in the presentinvention may have a single composition, or alternatively grains with aplurality of compositions may be also contained within the single layeror a plurality of layers.

To the silver halide grains to be used in the silver halide emulsion,there can be added metal ions by use of at least one selected fromcadmium salts, zinc salts, lead salts, thallium salts, iridium salts(complexes containing them), rhodium salts (complexes containing them)and iron salts (complexes containing them) in the process of formingand/or growing the grains to incorporate these metal elements internallyof the grains and/or on the grain surfaces, and a water-soluble rhodiumsalt is particularly preferably. Also, by placing in a reductiveappropriate atmosphere, reduced sensitizing nuclei can be impartedinternally of the grains and/or on the grain surfaces. When awater-soluble rhodium salt is added, the amount added may be preferably1×10⁻⁷ to 1×10⁻⁴ mole/1 mole AgX.

The silver halide grains to be used in the silver halide emulsion mayeither have a uniform silver halide composition distribution within thegrain or a core-shell grain with different silver halide compositions inthe inner portion and in the surface layer of the grain.

The silver halide grains to be used in the silver halide emulsion may beeither those in which latent images are formed primarily on the surfaceor those primarily internally of the grains.

The silver halide grains to be used in the silver halide emulsion may beeither those having regular crystal forms such as cubic, octahedral,tetradecahedral bodies, or irregular shapes such as spherical, plateshapes. Also, they may have composite form of these crystal forms, andmay contain grains of various forms mixed therein.

As the silver halide emulsion, two or more kinds of silver halideemulsions which have been formed separately may be used in a mixture.

The silver halide emulsion should be preferably sensitized by use ofchemical sensitizers and the sensitizing methods as described in G.B.Pat. Nos. 618,061, 1,315,755, 1,396,696, Japanese Patent Publication No.15748/1969, U.S. Pat. Nos. 1,574,944, 1,623,499, 1,673,522, 2,278,947,2,399,083, 2,410,689, 2,419,974, 2,448,060, 2,487,850, 2,518,698,2,521,926, 2,642,361, 2,694,637, 2,728,668, 2,739,060, 2,743,182,2,743,183, 2,983,609, 2,983,610, 3,021,215, 3,026,203, 3,297,446,3,297,447, 3,361,564, 3,411,914, 3,554,757, 3,565,631, 3,565,633,3,591,385, 3,656,955, 3,761,267, 3,772,031, 3,857,711, 3,891,446,3,901,714, 3,904,415, 3,930,867, 3,984,249, 4,054,457, 4,067,740 and TheTheory of the Photographic Process. 4th Ed. Macmillan. 1977 by T. H.James, page 67˜76.

The silver halide emulsion to be used in the light-sensitive materialaccording to the present invention can be chemically sensitized to arequired wavelength region by use of a dye which has been known as thesensitizing dye in the field of photography. The sensitizing dye may bealso used alone, but may be also used in combination of two or morekinds. Together with the sensitizing dye, there may be also contained asupersensitizer which is a dye having itself no spectral sensitizingaction, or a compound absorbing substantially no visible light, andpotentiating the sensitizing action of the sensitizing dye may be alsocontained in the emulsion.

As the useful sensitizing dye to be used in the blue-sensitive silverhalide nucleus emulsion layer, there may be included, for example, thoseas described in West German Pat. No. 929,080, U.S. Pat. Nos. 2,231,658,2,493,748, 2,503,776, 2,519,001, 2,912,329, 2,656,959, 3,672,897,3,694,217, 4,025,349, 4,046,572, G.B. Pat. No. 1,242,588, JapanesePatent Publication Nos. 14030/1969, 1977.

As the useful sensitizing dye to be used in the green-sensitive silverhalide emulsion, there may be included, for example, cyanine dyes,melocyanine dyes or complex cyanine dyes as described in U.S. Pat. Nos.1,939,201, 2,072,908, 2,739,149, 2,945,763, G. B. Pat. No. 505,979 asrepresentative ones.

Further, as the useful sensitizing dye to be used in the red-sensitivesilver halide emulsion, there may be included, for example, cyaninedyes, melocyanine dyes or complex cyanine dyes as described in U.S. Pat.Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,629, 2,776,280 asrepresentative ones. Also, cyanine dyes or complex cyanine dyes asdescribed in U.S. Pat. Nos. 2,213,995, 2,493,748, 2,519,001, West GermanPat. No. 929,080 can be advantageously used in the green-sensitivesilver halide emulsion or the red-sensitive silver halide emulsion.

In the silver halide emulsion to be used in the present invention, forthe purpose of preventing fog or maintaining photographic performancesduring the preparation steps, storage or photographic processing of thelight-sensitive material, a compound known as the antifoggant orstabilizer in the field of photography can be added during chemicalaging, on completion of chemical aging and/or after completion ofchemical aging before coating of the silver halide emulsion.

Examples of the antifoggant, stabilizer may include azaindenes such aspentazaindenes as disclosed in U.S. Pat. Nos. 2,713,541, 2,743,180,2,743,181, tetrazaindenes as disclosed in U.S. Pat. Nos. 2,716,062,2,444,607, 2,444,605, 2,756,147, 2,835,581, 2,852,375, ResearchDisclosure I4851, triazaindenes as disclosed in U.S. Pat. No. 2,772,146,polymerized azaindenes as disclosed in Japanese Unexamined PatentPublication No. 211142/1982; quaternary phosphonium salts such asthiazolium salts as disclosed in U.S. Pat. Nos. 2,131,038, 3,342,596,3,954,478, pyrylium salts as disclosed in U.S. Pat. No. 3,148,067, andphosphonium salts as disclosed in Japanese Patent Publication No.40665/1975; mercapto-substituted heterocyclic compounds such asmercaptotetrazoles, mercaptotriazoles, mercaptodiazole as disclosed inU.S. Pat. Nos. 2,403,927, 3,266,897, 3,708,303, Japanese UnexaminedPatent Publication Nos. 135835/1980, 71047/1984, mercaptothiazoles asdisclosed in U.S. Pat. No. 2,824,001, mercaptobenzthiazoles,mercaptobenzimidazoles as disclosed in U.S. Pat. No. 3,937,987;mercaptooxadiazoles as disclosed in U.S. Pat. No. 2,843,491,mercapto-substituted heterocyclic compounds such as mercaptothiadiazolesas disclosed in U.S. Pat. No. 3,364,028, polyhydroxybenzenes such ascatechols as disclosed in U.S. Pat. No. 3,236,652, Japanese PatentPublication No. 10256/1968, rezorcine as disclosed in Japanese PatentPublication No. 44413/1981, and gallic acid esters as disclosed inJapanese Patent Publication No. 4133/1968; heterocyclic compoundsincluding azoles such as tetrazoles as disclosed in West German PatentNo. 1,189,380, triazole as disclosed in U.S. Pat. No. 3,157,509,benztriazoles as disclosed in U.S. Pat. No. 2,704,721, urazoles asdisclosed in U.S. Pat. No. 3,287,135, pyrazoles as disclosed in U.S.Pat. No. 3,106,467, imidazoles as disclosed in U.S. Pat. No. 2,271,229,and azoles such as polymerized benzotriazoles as disclosed in JapaneseUnexamined Patent Publication No. 90844/1984, etc., pyrimidines asdisclosed in U.S. Pat. No. 3,161,515, 3-pyrazolidones as disclosed inU.S. Pat. No. 2,751,297, and heterocyclic compounds such as polymerizedpyrrolidones, namely polyvinyl pyrrolidones, etc. as disclosed in U.S.Pat. No. 3,021,213; various inhibitor precursors as disclosed inJapanese Unexamined Patent Publication Nos. 130929/1979, 137945/1984,140445/1984, G.B. Patent No. 1,356,142, U.S. Pat. Nos. 3,575,699,3,649,267; sulfinic acid, sulfinic acid derivatives as disclosed in U.S.Pat. No. 3,047,393; and inorganic salts as disclosed in U.S. Pat. Nos.2,566,263, 2,839,405, 2,488,709, 2,728,663.

Further, in all the hydrophilic colloid layers in the light-sensitivematerial to be used in the present invention, various additives forphotography can be used, if necessary, such as gelatin plasticizers,film hardeners, surfactants, image stabilizers, UV-ray absorbers,antistain agents, pH controllers, antioxidants, antistatic agents,thickeners, graininess improvers, dyes, mordants, brighteners,developing speed controllers, matte agents, etc., within the range whichdoes not impair the effect of the present invention.

In the light-sensitive material according to the present invention, apolymer latex should be preferably contained, and examples of thepolymer latex to be incorporated in said light-sensitive material mayinclude preferably hydrates of vinyl polymers such as acrylates,methacrylates, styrene, etc. as disclosed in U.S. Pat. Nos. 2,772,166,3,325,286, 3,411,911, 3,311,912, 3,525,620, Research Disclosure No. 195,19551 published in July, 1989.

As the polymer latex which may be preferably used, there may be includedhomopolymers of methaalkyl acrylate such as methyl methacryate, ethylmethacrylate, etc, homopolymers of styrene, or copolymers of methaalkylacrylate or styrene with acrylic acid, N-methylolacryl-amide, glycidolmethacrylate, etc., homopolymers of alkyl acrylate such as methylacrylate, ethyl acrylate, butyl acrylate, etc. or copolymers of alkylacrylate with acrylic acid, N-methylolacrylamide, etc. (preferably thecontent of the copolymer component such as acrylic acid, etc. being upto 30% by weight), homopolymers of butadiene or copolymers of butadienewith at least one of styrene, butoxymethylacrylamide acrylic acid,vinylidene chloride-methyl acrylate-acrylic acid ternary copolymer, etc.

The preferable range of the average particle size of the polymer latexto be used in the present invention may be 0.005 to 1μ, particularlypreferably 0.2 to 0.1μ.

The polymer latex to be used in the present invention may be containedeither on one surface with respect to the support or both surfaces. Morepreferably, it should be contained on both surfaces. When it iscontained on both surfaces with respect to the support, the kind and/orthe amount of the polymer latex contained on the respective surfaces maybe either the same or different:

The layer in which the polymer latex is added may be any layer. Forexample, when it is contained in the side containing the silver halidelight-sensitive layer with respect to the support, the polymer latex maybe contained in the silver halide light-sensitive layer, oralternatively in the non-light-sensitive colloid layer of the uppermostlayer which is generally called protective layer. Of course, when otherlayers, for example, intermediate layers exist between the silver halidelight-sensitive layer and the uppermost layer, it may be contained insuch intermediate layer. Further, the polymer latex may be contained ineither single layer in the surface comprising a plurality of layers orin plural layers (not limited to 2 layers) comprising any desiredcombination of layers.

As the binder in the light-sensitive material to be used in the presentinvention, gelatin is used, and this gelatin includes gelatinderivatives, etc., and also cellulose derivatives, graft polymers ofgelatin with other polymers, and other proteins, sugar derivatives,cellulose derivatives, hydrophilic colloids of synthetic hydrophilicpolymeric substances, etc. which may be either of homopolymers orcopolymers can be also used in combination.

As gelatin, in addition to lime-treated gelatin, acid-treated gelatin,enzyme-treated gelatin as described in Bulletin of Society of SciencePhotography of Japan (Bull. Soi. Sci. Phot. Japan) No. 16, p. 30 (1966)may be also used, and also hydrolyzates or enzyme decomposed products ofgelatin can be used. As the gelatin derivatives, there may be employedthose obtained by reacting various compounds such as acid halide, acidanhydride, isocyanates, bromoacetic acid, alkanesulfones,vinylsulfonamides, maleinimide compounds, polyalkylene oxides, epoxycompounds, etc. with gelatin. Specific examples are disclosed in U.S.Pat. Nos. 2,614,928, 3,132,945, 3,186,846, 3,312,553, G.B. Patent Nos.861,414, 1,033,189, 1,005,784, Japanese Patent Publication No.26845/1967.

As the protein, albumin, casein, as the cellulose derivative,hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulphate oras the sugar derivative, sodium alginate, starch derivative may be alsoused in combination with gelatin.

As the above-mentioned graft polymer of gelatin with other polymers,those having homo- or copolymer of a vinyl type monomer such as acrylicacid, methacrylic acid, derivatives thereof such as ester, amide, etc.,acrylonitrile, styrene, etc. grafted onto gelatin can be used.Particularly, graft copolymers of polymers compatibility to some extentwith gelatin, such as polymers of acrylic acid, acrylamide,methacrylamide, hydroxyalkyl methacrylate, etc. are preferred. Examplesof these are disclosed in U.S. Pat. Nos. 2,763,625, 2,831,767,2,956,884.

The amount of gelatin coated, when containing no polymer latex otherthan subbing layer on the surface corresponding to the surface of thelight-sensitive material, may be preferably 1.8 g/m² to 5.5 g/m²,particularly 2.0 to 4.8 g/m² per one surface of the support. When apolymer latex is contained on that surface, it should be preferably 1.5to 6.0 g/m², particularly preferably 1.8 to 5.5 g/m².

The support to be used in the light-sensitive material of the presentinvention may include flexible reflective support such as paperslaminated with α-olefin polymer (e.g. polyethylene/butene copolymer),etc., synthetic papers, etc., films comprising semi-synthetic orsynthetic polymers such as cellulose acetate, cellulose nitrate,polystyrene, polyvinyl chloride, polyethylene terephthalate,polycarbonate, polyamide, etc., and flexible supports having reflectivelayer provided on these films, metal, etc.

Among them, polyethylene terephthalate is particularly preferred.

As the subbing layer which can be used in the present invention, theremay be included the subbing working layer in organic solvent systemcontaining polyhydroxybenzenes as disclosed in Japanese UnexaminedPatent Publication No. 3972/1984, etc., aqueous latex subbing workinglayers as disclosed in Japanese Unexamined Patent Publication No.11118/1974, 104913/1977, 19941/1984, 19940/1984, 1984, 112326/1976,117617/1976, 58469/1976, 114120/1976, 121323/1976, 123129/1976,114121/1976, 139320/1977, 65422/1977, 109923/1977, 119919/1977, 1980,128332/1982, 19941/1984.

Also, said subbing layer can be generally subjected on its surface tochemical or physical treatment. As said treatment, there may be includedsurface activating treatments such as chemical treatment, mechanicaltreatment, corona dicharging treatment, flame treatment, UV-raytreatment, high frequency treatment, glow discharging treatment, activeplasma treatment, laser treatment, mixed acid treatment, ozone oxidationtreatment, etc.

The subbing layer is distinguished from the coating layer according tothe present invention and the coating timing and conditions are notlimited at all.

In the present invention, filter dyes and other dyes for variouspurposes such as halation prevention can be used. The dyes employed mayinclude triaryl dyes, oxanol dyes, hemioxanol dyes, malocyanine dyes,cyanine dyes, styryl dyes, azo dyes. Among them, oxanol dyes, hemioxanoldyes and melocyanine dyes are useful. Specific examples of the dyeswhich can be used may include those as disclosed in West German PatentNo. 616,007, G.B. Patent Nos. 584,609, 1,177,429, Japanese PatentPublication Nos. 7777/1951, 1964, 38129/1979, 85130/1973, 99620/1974,111420/1974, 129537/1974, 28827/1975, 108115/1977, 185038/1982,24845/1984, U.S. Pat. Nos. 1,878,961, 1,884,035, 1,912,797, 2,098,891,2,150,695, 2,274,782, 2,298,731, 2,409,612, 2,461,484, 2,527,583,2,533,472, 2,865,752, 2,956,879, 3,094,418, 3,125,448, 3,148,187,3,177,078, 3,247,127, 3,260,601, 3,282,699, 3,409,433, 3,540,887,3,575,704, 3,653,905, 3,718,472, 3,865,817, 4,070,352, 4,071,312, PBreport No. 74175, Photo Abstr. 128 (1921).

Particularly, in film for daylight contact work light-sensitivematerial, these dyes should be preferably used, and it is particularlypreferable to use them so that the sensitivity to the light of 400 nmmay be incorporated to 30-fold or more of the sensitivity to the lightof 360 nm.

Further, in the practice of the present invention, it is also possibleto use an organic desensitizer with the sum of the anode potential andthe cathode potential of polarography being positive as described inJapanese Unexamined Patent Publication No. 26041/1986.

The light-sensitive material of the present invention can be exposed byuse of an electromagnetic wave in the spectral region to which theemulsion layer constituting said light-sensitive material hassensitivity.

The present invention can give remarkable effect when applied to alight-sensitive material for printing for which very high dimensionalstability before and after processing is required.

The developing agent to be used in development of the light-sensitivesilver halide photographic material according to the present inventionmay include those as mentioned below.

Representative of the HO--(CH═CH)_(n) --OH type developing agents arehydroquinone, and otherwise catechol, pyrogallol and their derivatives,and also ascorbic acid, chlorohydroquinone, bromohydroquinone,methylhydroquinone, 2,3-dibromohydroquinone, 2,5-diethylhydroquinone,catechol, 4-chlorocatechol, 4-phenylcatechol, 3-methoxy-catechol,4-acetyl-pyrogallol, sodium ascorbate.

As the heterocyclic type developer, there may be included3-pyrazolidones such as 1-phenyl-3-pyrazolidone,1-phenyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone;1-phenyl-4-amino-5-pyrazolone, 5-aminouracil, etc.

Otherwise, the developers as described in T. H. James The Theory of ThePhotographic Process, Fourth Edition), p. 291-334 and Journal of theAmerican Chemical Society, vol. 73, p. 3,100 (1951) can be effectivelyused in the present invention. These developing agents can be usedeither singly or as a combination of two or more kinds, but preferablytwo or more kinds may be used in combination.

Also, in the developer to be used for development of the light-sensitivematerial, as the preservative, for example, a sulfite such as sodiumsulfite, potassium sulfite, etc. can be used without impairing theeffect of the present invention. Also, hydroxylamine, a hydrazidecompound can be used as the preservative, and in this case, its amountmay be preferably 5 to 500 g, more preferably 20 to 200 g per one literof the developer.

Also, in the developer may be contained glycols as an organic solvent,and as such glycol, ethylene glycol, diethylene glycol, propyleneglycol, triethylene glycol, 1,4-butanediol, 1,5-pentane diol, etc. maybe preferably used. The amount of these glycols used may be 5 to 500 g,more preferably 20 to 200 g per one liter of the developer. Theseorganic solvents can be used either alone or in combination.

The light-sensitive silver halide photographic material according to thepresent invention can be subjected to developing processing by use of adeveloper containing a development inhibitor, whereby a light-sensitivematerial very excellent in storage stability can be obtained.

The light-sensitive silver halide photographic material according to thepresent invention can be processed under various conditions. Theprocessing temperature may be, for example, a developing temperature of50° C. or lower, particularly around 25° to 40° C., and also thedeveloping time should be preferably completed within less than 20seconds, particularly 19 seconds or less. Further, the present inventioncan exhibit its effect most effectively when the developing time iswithin the range of 15 seconds or less, and further 15 to 10 seconds.

Other processing steps than developing, for example, water washing,stopping, stabilizing, fixing, and further previous film hardening,neutralization, etc. can be employed as desired, and these can be alsosuitably omitted.

In the present invention, in the fixer which can be used duringprocessing, in addition to thiosulfate, sulfite, etc., various acids,salts, fixing promoters, humectants, surfactants, chelating agents, filmhardeners, etc. can be contained. For example, there may be included asthiosulfates, sulfites, potassium, sodium, ammonium salts of theseacids, as acids, sulfuric acid, hydrochloric acid, nitric acid, boricacid, formic acid, acetic acid, propionic acid, oxalic acid, tartaricacid, citric acid, malic acid, phthalic acid, etc. and as salts,potassium, sodium, ammonium salts, etc. of these acids. As the fixingpromoter, there may be included thiourea derivatives, alcohols havingtriple bond within the molecule as disclosed in Japanese PatentPublication No. 35754/1970, Japanese Unexamined Patent Publication Nos.122535/1983, 122536/1983, thioethers, as disclosed in U.S. Pat. No.4,126,459, or cyclodextran ethers which make free anions, crown ethers,diazabicycloundecene, di(hydroxyethyl)butamine, etc. As the humectant,alkanolamines, alkylene glycols, etc. may be included. As the chelatingagent, aminoacetic acids such as nitrilotriacetic acid, EDTA, etc. maybe included. As the film hardener, chromium alum, potassium alum, andother Al compounds, etc. can be incorporated.

The present invention can exhibit its advantages greatly when ultra-fastprocessing with a processing time of 20 to 60 seconds is applied.Although such ultra-fast processing has been desired, the ultra-fastprocessing as mentioned in the present specification refers to aprocessing in which the total time after the tip end of a film isinserted into an automatic developing machine, passing through thedeveloping tank, the cross-over portion, the fixing tank, the cross-overportion, the water washing tank, the cross-over portion, the dryingportion, until the tip end of the film comes out from the drying portion(in other words the quotient of the entire length of the processing linedivided by the line conveying speed) is 20 seconds to 60 seconds. Here,the reason why the time at the cross-over portions is included, as iswell known in this field of art, because the processing steps areregarded to substantially proceed, since the liquid in the precedingprocess is swelled in the gelatin film also in the cross-over portion.

The present invention is described in detail by referring to Examples,by which the present invention is not limited at all.

EXAMPLE 1

An aqueous silver nitrate solution and an aqueous solution of sodiumchloride and potassium bromide were mixed in an aqueous gelatin solutionat pAg=7.7 by use of the control double jet method to form silver halidegrains, followed by desalting in conventional manner to obtain a silverhalide emulsion. The silver halide emulsions obtained at this time areshown in Table 1.

                  TABLE 1                                                         ______________________________________                                               Halide composition                                                                          Average grain                                            Emulsion                                                                             Cl/Br         size μm  Crystal habit                                ______________________________________                                        A      98/2          0.12        Cubic                                        B      70/30         0.22        "                                            C       0/100        0.25        "                                            ______________________________________                                    

Then, 1.2 g of the hydrazine compound shown in Table 2 was added to theemulsion A per 1 mole of silver. Further, as the antifoggant, 30 mg/m²of 1-phenyl-5-mercaptotetrazole and 20 mg/m² of 5-methylbenzotriazole,as the development controller, 30 mg/m² of a nonylphenoxy-polyethyleneglycol (ethylene oxide units 30) and 1 g/m² of an acrylic acid-butylmethacrylate-styrene polymer latex, and further bisvinylsulfomethylether and glyoxazole of the film hardening agent were successivelyadded, and the resultant mixture was coated on a polyethyleneterephthalate base simultaneously with a protective layer. The gelatinamount relative to the silver amount is shown in Table 2. Then, thesesamples were exposed through a glass wedge by P-627 FM roomlight printer(manufactured by Dainippon Screen), and processed with the developer andthe fixed shown below. In this processing, developing time was 15seconds (35° C.).

    ______________________________________                                        <Developer recipe>                                                            Hydroquinone                34     g                                          N-methyl-p-aminophenol      0.23   g                                          Disodium ethylenediaminetetraacetate                                                                      1      g                                          3-Diethylamino-1,2-propane diol                                                                           15     g                                          5-Methylbenztriazole        0.4    g                                          Na.sub.2 SO.sub.3           76     g                                          NaBr                        3      g                                          NaCl                        1.3    g                                          1 mole/phosphoric acid solution                                                                           400    ml                                         (after addition of NaOH necessary for adjustment                              to pH 11.5, made up to one liter with water)                                  <Fixer recipe>                                                                (Composition A)                                                               Ammonium thiosulfate (72.5% W/V aqueous solution)                                                         240    ml                                         Sodium sulfite              17     g                                          Sodium acetate trihydrate   6.5    g                                          Boric acid                  6      g                                          Sodium citrate dihydrate    2      g                                          (Composition B)                                                               Pure water (deionized water)                                                                              17     ml                                         Sulfuric acid (50% W/V aqueous solution)                                                                  4.7    g                                          Aluminum sulfate (8.1% W/V aqueous solution                                                               26.5   g                                          as calculated on Al.sub.2 O.sub.3)                                            ______________________________________                                    

During use of the fixer, the above compositions A and B During use ofwere dissolved in this order in 500 ml of water and then made up to oneliter before use. The pH of the fixer was adjusted to 6 with aceticacid.

The amount of the silver coated was analyzed by a fluorescent X-rayanalyzer.

The silver amount after processing is shown in the silver amount whichgives the maximum density.

                                      TABLE 2                                     __________________________________________________________________________             Gelatin amount                                                                        Gelatin amount                                                        in emulsion                                                                           in protective                                                                         Coated silver                                                                        Developed                                        Hydrazine                                                                           layer   layer   amount silver amount                                                                           The present                         No.                                                                              compound                                                                            (g/m.sup.2)                                                                           (g/m.sup.2)                                                                           (g/m.sup.2)                                                                          (g/m.sup.2)                                                                          γ                                                                          invention                           __________________________________________________________________________    1  I-2   1.0     0       2.0    2.0    12.0                                                                             ◯                       2  "     "       0.2     "      1.9    11.4                                                                             ◯                       3  "     1.3     0.2     "      2.0    10.3                                                                             ◯                       4  "     "       0.9     "      1.5     6.8                                                                             X                                   5  "     1.0     0.2     3.0    3.0    12.0                                                                             ◯                       6  "     "       0.7     "      2.8    11.2                                                                             ◯                       7  "     1.5     0.7     "      2.9    10.3                                                                             ◯                       8  "     "       1.7     "      2.9     6.5                                                                             X                                   9  "     2.0     0.5     4.0    3.9    11.8                                                                             ◯                       10 "     "       1.2     "      3.8    11.2                                                                             ◯                       11 "     "       2.4     "      2.8     6.5                                                                             X                                   12 "     3.0     0.5     "      3.8    11.3                                                                             ◯                       13 "     "       1.5     "      2.9     6.3                                                                             X                                   14 --    3.0     0.5     "      3.6     5.4                                                                             X                                   __________________________________________________________________________

γ is defined for density from 0.3 to 3.0.

The product with γ<6 can be practically applied with difficulty becausefine lines are practically collapsed.

As is apparent from Table 2, it can be understood that 90% or more of Agcoated was developed, and also a high contrast image with γ of 6 or moreis given, when the ratio of the silver amount to gelatin is 1.0 or more.

EXAMPLE 2

To the emulsion B subjected to gold-sulfur sensitization was added 1.2 gof the hydrazine compound shown in Table 3 and also 300 mg of thesensitizing dye shown below per one mole of silver, followed by coatingsimilarly as in Example 1. The gelatin amount relative to the silveramount is shown in Table 3. These samples were subjected to wedgeexposure by xenon light, and processed similarly as in Example 1.##STR18##

                                      TABLE 3                                     __________________________________________________________________________             Gel amount                                                                          Gel amount                                                                          Coated                                                                            Developed                                                     in emulsion                                                                         in protec-                                                                          silver                                                                            silver   Dot                                            Hydrazine                                                                           layer tive layer                                                                          amount                                                                            amount   quality                                                                           The present                             No.                                                                              compound                                                                            (g/m.sup.2)                                                                         (g/m.sup.2)                                                                         (g/m.sup.2)                                                                       (g/m.sup.2)                                                                         γ                                                                          rank                                                                              invention                               __________________________________________________________________________    1  I-1   1.0   0     2.0 2.0   11.9                                                                             5   ◯                           2  "     "     0.2   "   1.9   11.4                                                                             5   ◯                           3  "     1.5   0.3   "   1.9   11.3                                                                             4   ◯                           4  "     "     0.7   "   1.5    6.8                                                                             2   X                                       5  "     2.0   0.5   3.0 2.9   10.9                                                                             5   ◯                           6  "     "     1.2   "   2.5    6.8                                                                             2   X                                       7  "     2.5   0.4   "   2.7   10.5                                                                             4   ◯                           8  "     "     1.0   "   2.3    6.4                                                                             2   X                                       9  "     3.0   0.5   4.0 3.8   10.2                                                                             4   ◯                           10 "     "     1.2   "   3.4    6.0                                                                             2   X                                       11 --    3.0   0.5   "   3.7    5.3                                                                             1   X                                       __________________________________________________________________________

The dot quality was evaluated based on the sensory examination byenlarging the dot formed by bringing the contact screen in close dotcontact with the film during exposure with a 100-fold magnifier.

The rank 5 indicates the highest state, with the states of rank 2 orlower standing no practical application.

From Table 3, it can be understood that 90% or more of the silver coatedis developed and also γ is 6.0 or more, when the ratio of the silveramount to the gelatin amount is 1.0 or more.

EXAMPLE 3

To the emulsion of C applied with gold-sulfur sensitization, 1.2 g ofthe hydrazine compound shown in Table 4 was added per one mole ofsilver, and 200 mg of the sensitizing dye shown below per one mole ofsilver, followed by coating similarly as in Example 1. The amount of thegelatin amount relative to the silver amount is shown in Table 4. Thesesamples were subjected to wedge exposure by xenon light, and processedsimilarly as in Example 1. ##STR19##

                                      TABLE 4                                     __________________________________________________________________________             Gel amount                                                                          Gel amount                                                                          Coated                                                                            Developed                                                     in emulsion                                                                         in protec-                                                                          silver                                                                            silver   Dot                                            Hydrazine                                                                           layer tive layer                                                                          amount                                                                            amount   quality                                                                           The present                             No.                                                                              compound                                                                            (g/m.sup.2)                                                                         (g/m.sup.2)                                                                         (g/m.sup.2)                                                                       (g/m.sup.2)                                                                         γ                                                                          rank                                                                              invention                               __________________________________________________________________________    1  I-1   1.0   0     2.0 2.0   11.9                                                                             5   ◯                           2  "     "     0.2   "   1.9   11.3                                                                             5   ◯                           3  "     1.5   0.2   "   1.9   11.2                                                                             4   ◯                           4  "     "     0.7   "   1.5    6.7                                                                             2   X                                       5  "     2.0   0.5   3.0 2.9   10.8                                                                             5   ◯                           6  "     "     1.2   "   2.5    6.5                                                                             2   X                                       7  "     2.5   0.2   "   2.7   10.3                                                                             4   ◯                           8  "     "     0.7   "   2.3    6.2                                                                             2   X                                       9  "     3.0   0.5   4.0 3.8   10.0                                                                             4   ◯                           10 "     "     1.2   "   3.4    6.0                                                                             2   X                                       11 --    "     0.5   "   3.7    5.1                                                                             1   X                                       __________________________________________________________________________

From Table 4, it can be understood that 90% or more of the silver amountcoated is developed, and γ is 6.0 or more and also the dot quality isexcellent, when the ratio of the silver amount to gelatin is 1.0 ormore.

I claim:
 1. A negative type light-sensitive silver halide photographicmaterial for producing a high contrast image in a developing processwherein the photographic material is in the developer for 19 seconds orless, said negative type light sensitive silver halide photographicmaterial comprising light-sensitive silver halide emulsion provided on asupport, wherein the ratio of silver amount to gelatin amount (Ag/Gel)(wherein said silver amount is the total silver amount in one or morelayers provided in the same side as said light-sensitive silver halideemulsion layer with respect to the support, and said gelatin amount isthe total gelatin amount in one or more gelatin layers provided in thesame side as said light-sensitive silver halide emulsion layer withrespect to the support) is 1.0 or more, and a hydrophilic colloid layerin said light-sensitive silver halide emulsion contains a hydrazinecompound of the Formula (I-b) shown below: ##STR20## wherein R₂₁represents an aliphatic group, an aromatic group or a heterocyclicgroup, R₂₂ represents hydrogen atom, an alkoxy group, a heterocyclic oxygroup, an amino group or an aryloxy group, P₁ and P₂ each representhydrogen atom, an acyl group or a sulfinic acid group.
 2. The negativetype light-sensitive photographic material according to claim 1, whereinsaid hydrazine compound is one of the following compounds: ##STR21## 3.The negative type light-sensitive silver halide photographic materialaccording to claim 1, wherein said hydrazine compound is used in anamount of 10⁻⁵ to 10⁻¹ mole/1 mole of silver.
 4. The negative typelight-sensitive silver halide photographic material according to claim1, wherein the amount of said gelatin coated, when containing no polymerlatex other than subbing layer on the surface corresponding to thesurface of the light-sensitive material, is 1.8 g/m² to 5.5 g/m², andwhen a polymer latex is contained on that surface, is 1.5 to 6.0 g/m².5. In a method of developing a negative type light-sensitive silverhalide photographic material wherein the negative type light-sensitivesilver halide material is subjected to a developing step in a developer,followed by stopping, stabilizing and fixing, the improvement whereinthe developing step is for 19 seconds or less and the negative-typelight sensitive silver halide material comprises light-sensitive silverhalide emulsion provided on a support, wherein the ratio of silveramount to gelatin amount (Ag/Gel) (wherein said silver amount is thetotal silver amount in one or more layers provided in the same side assaid light-sensitive silver halide emulsion layer with respect to thesupport, and said gelatin amount is the total gelatin amount in one ormore gelatin layers provided in the same side as said light-sensitivesilver halide emulsion layer with respect to the support) is 1.0 ormore, and a hydrophilic colloid layer in said light-sensitive silverhalide emulsion contains a hydrazine compound of the formula (I-b) shownbelow: ##STR22## wherein R₂₁ represents an aliphatic group, an aromaticgroup or a heterocyclic group, R₂₂ represents hydrogen atom, an alkoxygroup which may be substituted, a heterocyclic oxy group, an amino groupor an aryloxy group, P₁ and P₂ each represent hydrogen atom, an acylgroup or a sulfinic acid group.
 6. The method of developing a negativetype light-sensitive silver halide photographic material according toclaim 5, wherein said hydrazine compound is used in an amount of 10⁻⁵ to10⁻¹ mole/mole of silver.
 7. The method of developing a negative typelight-sensitive silver halide photographic material according to claim5, wherein the amount of said gelatin coated, when containing no polymerlatex other than subbing layer on the surface corresponding to thesurface of the light-sensitive material, is 1.8 g/m² to 5.5 g/m² andwhen a polymer latex is contained on that surface, is 1.5 to 6.0 g/m².8. The method of claim 5, wherein the developing time is 15 seconds orless.
 9. The method of claim 8, wherein the developing time is 10 to 15seconds.